Total Synthesis of (−)‐Daphenylline. (8th April 2016)

• Record Type: Journal Article
• Authors: Yamada, Ryosuke; Adachi, Yohei; Yokoshima, Satoshi; Fukuyama, Tohru
• Is Part Of: Angewandte Chemie. Volume 128:Number 20(2016)
• Page Start: 6171
• Page End: 6174
• Publication Date: 2016-04-08
• Subjects: Alkaloide -- Cycloadditionen -- Naturstoffe -- Stereoselektive Synthesen -- Umlagerungen; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201601958
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: Total synthesis of (−)‐daphenylline, a hexacyclic Daphniphyllum alkaloid, was achieved. Construction of the tricyclic DEF ring system was initiated by asymmetric Negishi coupling followed by an intramolecular Friedel–Crafts reaction. Installation of a side chain onto the tricyclic core was carried out through Sonogashira coupling, stereocontrolled Claisen rearrangement by taking advantage of the characteristic conformation of the tricyclic DEF core, and the stereoselective alkylation of a lactone. After the introduction of a glycine unit, the ABC ring system was stereoselectively constructed through intramolecular cycloaddition of the cyclic azomethine ylide. Abstract : Ringe schmieden Ringe : Die Totalsynthese von Daphenyllin, einem hexacyclischen Daphniphyllum ‐Alkaloid umfasst eine Claisen‐Umlagerung mit ferngesteuerter Stereokontrolle, die sich auf die charakteristische Konformation des tricyclischen DEF‐Strukturkerns stützt. Zusätzlich erzeugt die intramolekulare Cycloaddition eines cyclischen Azomethin‐Ylids das ABC‐Ringsystem.